Textile decorating compositions



Patented Feb. 25, 1941 TEXTILE DECORATING COMPOSITIONS David M. Gans, New York, N. Y., and John R.

Abrams, Jersey City, N. 1., asslgnors to Interchemical Corporation, New York, N. Y., a corporation of Ohio No Drawing. Application May 28, 1941,

Serial No. 395,610

4 Claims. (01. 260-29) This invention relates to textile decorating compositions, and is directed particularly to such compositions which contain pigments dispersed in resins of the type which are convertible to the insoluble and infusible state by heat or otherwise.

Specifically, this invention relates to such compositions in which extremely good printing properties, high color value, and the like, are obtained by a conversion of the resin solution to the state of incipient gelation, in which the resin solution employed is no longer in a flowable liquid state.

Conventional textile printing is ordinarily done with water solutions of dyestuffs containing water soluble thickening agents in'sufllcient quantity to retard the spreading of the color on the fabric after printing. The dyestufi is fixed onto the fabric by some chemical process, and the thickening agent is then washed out of the fabric. The time and expense involved in this after treatment, added to the originally high color cost for light and tub-fast dyes, has been a major problem in textile printing. An unsolved. problem hasbeen the reproduction of very fine designs. Since the pastes spread on the fabric after printing when thin enough to be removed sharply from fine engravings, giving blurred designs, it has been found impossible to use photogravure cylinders or extremely fine mill and die engravings. Attempts to modify these pastes by addition of wetting agents and emulsification of oils therein have not solved the basic difllculties.

The use'as printing pastes of colored lacquers (which, for the purpose of this application are defined as dispersions of color in vehicles consisting of a solution of a plastic or solid film-forming, water-resistant binder such as a cellulose derivative or a resin, in anorganic solvent or mixture of solvents) has been attempted in order to overcome the difliculties with prior art pastes, but has not been successful commercially. Relatively few lacquer compositions withstand both dry cleaning and washing; and such compositions as are resistant have been generally unacceptable due to the fact that the fabrics, when printed with these lacquers, develop an undesirable stifl feel (known to the trade as "hand), to the necessity for using large amounts of color to obtain deep shades, and to the tendency of colored markings to rub oil onto other clothing and leaves. mark (known as fcrocking) In the Jenett U. 5. Patent No. 2,222,581, there is described a new type of textile printing paste which eliminates the disadvantages of the conventional dye printing pastes and avoids the dif- ,flculties which have been encountered in the prior art lacquer printing pastes. These new astes are emulsions in which an outer continuous water-immiscible-lacquer phase is thickened by an inner aqueous phase which is at least 20 per cent. of the total emulsion, by weight. Preferably, the binder of the lacquer is one which is originally soluble in ordinary organic solvents and which can be converted into an insoluble state after printingmost desirably, a readily heat-polymerizable synthetic resin, best exemplified by urea formaldehyde and allied resins.

The use of pastes made in accordance with this imparted to fabrics by these pastes is very much less than the hand imparted to similar fabrics by ordinary lacquer pastes having the same binder, the amount of color needed to produce deep shades is sharply reduced, and the crocking substantially eliminated.

We have discovered that pigmented pastes of the type described in the said patent can be markedly improved, particularly with respect to the color value obtainable therefrom, by treating the pastes, or the resin solutions used in making the pastes, to bring the resin solution to a state of partial gelation. In this state, the resin solutions are no longer true liquids, but have the peculiar mucilaginous consistency and 'flow characteristic of egg whites, in which smooth gelatinous masses appear to be dispersed through a rather thick liquid; and these pastes are thus essentially dispersions of gelled resin in resin solution.

Surprisingly enough, this type of printing paste wipes into, and separates from the cells of an intaglio engraving, just as smoothly and easily as a perfectly smooth flowing ink, even though the pastes may flow only fitfully through a tube because of the presence of gelled masses in the body thereof.

If the resin solutions are converted to harder gels, where they approach the consistency of egg whites which have been heated, thereby increasing the size and number of the smooth gelatinous masses dispersed therein, the pastes can be thickened sufficiently by the presence of this gelled resin-solvent combination so that the amount of water necessary for optimum printing properties can be reduced, and in some cases the water can be eliminated.

In determining whether or not the gelation has been carried to a. sufllcientstate to permit of the partial or total removal of water, the viscosity and yield value of the finished paste are of considerable value. The viscosity should be low (0.1 to 20 poises at 25 C.) and the yield value high (at least 50 dynes per square cm.) in order to get the desired printing properties. Preferably, we prefer to operate in a range of yield values between 100 and 800 dynes per square centimeter.

In some cases, the compositions sh'ow pseudoplasticity, and therefore have no true yield value and viscosity; however, the flow curves of these compositions reveal apparent values approximating those given above for true plastic compositions. I

It is important that the gelation be controlled so that the entire mass does not set up to a stiif gel which cannot be dispersed in resin solution. This can be easily avoided by controlling the time of treatment, and the reactants employed.

The carrying of the resin to the state of incipient gelation has still another value-it shortens the time required when the fabric is dried after printing to complete the conversion of the resins to the desired insoluble and infusible condition, so that unusually good wash-resistance can be obtained even in the absence of a prolonged cure of the resin.

Typical examples of our invention are the following:

Example 1 Parts by weight Solvent-soluble urea formaldehyde resin 3.75 Alkyd resin (glycerol phthalate modified with 35% soya oil) 11.25 Toluene 11.25 Solvent for urea resin:

Xylene 1.50

Butanol 2.25 Pine o 7.00 Solvesso #3 (hydrogenated petroleum naphtha-boiling range 182-210 C.) 53.00 Indanthrene Blue (vat pigment) 2.00 Alumina Aerogel 8.00

The ingredients are ball milled for 72 hours.

After ageing for nine days, this paste showed:-

C.750 dynes per square centiphenyl methyl pyrazolone dicarboxylic acid.

The gelation in this case is probably caused by the exposure of the alkyd and urea formaldehyde resins to gelling reactants which are present in small quantities in all binders, in the presence of the alumina aerogel, which has an extremely high specific surface, and which may contain acid or similar adsorbed impurities. Similar results are obtained with other aerogels, such as silica. aerogel; the aerogels may be produced in accordance with the disclosure of the Kistler Patent 2,093,454, September 21,1937. Some gelation occurs with either the alkyd or the urea resin alone; but we prefer to use both, because the gelation occurs more rapidly and smoothly when, both are present.

The paste prints well, and gives prints which may be set more rapidly than ungelled prints.

The ingredients are ball milled for 72 hours, with the exception of the trichloracetic acid, which is dissolved in part of the Solvesso #3 saved out for this purpose, and added at the end of the ball milling operation. I

Four days after it was made, this paste showed:

Yield value at C.125 dynes per square centimeter Viscosity at 25 C.-0.5 poises When 11 days old, the yield value was 235 dynes per square centimeter, which shows the paste to be quite stable. The paste had the typical mucilaginous structure of a gel dispersed in' a resin solution. On printing, the paste can be set by mere ageing, or by a very short heating.

This ink has been converted to the state of partial gelation by the use of trichloraceticacid. Other acids can be used toreplace itfor example, dichlor'acetic, phthalic, tartaric, maleic, salicylic and similar acids soluble in the solvent employed.

The emulsion printing pastes of the J enett Patent No. 2,222,581, can also be improved by converting the resin solution to the state of partial gelation, to get a dispersion of gelled resin in ungelled resin. The addition of acid as described in Example 2 is useful in this regard; the application of the method to emulsions has the advan- .45 tage that the non-aqueous paste can be carried to the state of gelation desired, and water containing a neutralizing agent can then be emulsified into it to stop further progress of the gelation.

If desired, the resin solution may be gelled first,

and the pigment pulp mixed in afterward.

Thus- Example 3 61 parts by weight of a 65% xylene solution of the alkyd resin of Example 1, 38 parts by weight of a 50% solution of the urea resin of Example 1 in 40-xylene-60-butanol, and 1 part by weight normal-butyl-hydrogen phosphate were heated to C. for twenty minutes, and allowed to stand overnight to form a rather stiif solvent-dispersible gel. The gel is mixed to form a, color by blending:

. Parts Gel 30 65 Pine oil 20 Turpentine 20 and emulsifying the mixture with:

' Parts 20% copper phthalocyanine aqueous pulp 20 0 Water 10 This gives a blue paste containing 4% of color, which has a color value substantially higher than a similar ungelled emulsion paste containing un- .75 gelled resin with the same amount of water.

- Similar gels to those ofExample 3 can be pre- These printing pastes can also be used. for ared by heating with acetic acid, etc., and with pigment dyeing; in this field, the pastes are used aqueous solutions ofsome electrolytes (e. g.20/ at relatively. iow binder content (preferably sodium chloride solution). v about 2%% or less) obtained by the use oflow- Both the non-aqueous and aqueous emulsion 5 solids reducing emulsions. The pastes are forced pigmented partial gels may be blended with clear through the cloth by pressure; on drying, the water-in-lacquer reducing emulsions (gelled or resin-pigment aggregates stick to the fibers ungelled) to obtain finished pastes of very acceptthroughout the threads in an even fashion, withable properties. Most desirably, they are blendout undue cementing. The use of water-ined with emulsions very low in solids content (of lacquer emulsions noteably reduces themigrathe order of 1%) which consist of water emulsition of color on drying, and substantially elimfled into lacquers consisting essentially of solvent inates this most serious difficulty in pigment and suiiicient film-former to stabilize the emuldyeing; the partial gelation of the resin further sion, the solvent being of a type which is a solvent increases this resistance to migration noteably.

for the resin of the pigmented paste when used While the examples are restricted to urea in limited quantities with relation to the resin, formaldehyde and alkyd resins together, these but which precipitates the resin-when used in resins may be gelled separately. Moreover, we excessive amounts. When blended with substanhave successfully obtained similar gels with tial quantities of such low-solids emulsions, the various heat-convertible carbamide-aldehyde resin-pigment-solvent aggregates separate out of resins (made from carbamides such as urea and the continuous phase, so that a three-phase mulits derivatives and related. compounds, including sion comesinto being. These emulsions consist thiourea, guanidine, m thyiol urea, melamine, of a continuous phase of resin solution rather biuret, other heat-convertible alkyd resins, low in solids, and a discontinuous aqueous phase, phenol fo maldehyde resins and the like.

with resin-pigment-solvent aggregates in suspen- Similarly. the Solvents and plasticizers y be sion in the continuous phase as well. Where a. changed as desired, e pigments should be partially gelled pigmented material is 'used in h s n W care. having in m n the light-fastaccordance with our invention, the gelled resin n ss an washrfastness requirements of the par- I A solution of: 50 alkydresin, 15 pine oil,

exists, in combination with solvent and pigticular problem. Furthermore, the water used t, i suspension i thi y t in the emulsion may be replaced by non-miscible An example of a clear reducing emulsion which Organic l q id in known manner. will yield a three phase emulsion with the prod- Obviously, the examples n e tiplied inuct of Example 3 is the following: definitely, without departing from the scope of Exam 1e 4 the invention, which is defined in the claims,

1) In both the printing and pigment dyeing oper-' A lacquer is made by mixing ations, it is noteworthy that the resultant fabric obtained is substantially like a dye-colored fab- Parts by weight ric, retaining its complete permeability to air,

35 solvesso #3 1'20 and to cleaning liquids. This result distinguishes 40 the textile decorating compositions herein dis- 4 3: 21:23 3 3 332 1: ggszifig f g closed from the various textile coating composimnge 135477, c 4 1 00 tions used to produce continuous films of fabric, solvesso #2 22:00 for water-proofing, artificial leather production,

and the like. We prefer to define our result as Into thislacquer is emulsified a mixture of: the production of microscopically discontinuous Parts by weight decorations on the cloth while producing visual Sodium chloride 0.15 mntmuity- 35% sulfonated tannin solution 0.12 We claim.

Acetic Mid 0.06 1. A textile decorating composition of plastic water 7547 consistency such that it can be applied to cloth by. intaglio printing plates to produce, when admono mixed witlli1 pigment, visually continuous but microscopica y discontinuous decorations on cloth.

Th a yd resin is a 4 TY 011 modified which comprises'a vehicle comprising a heat-conly oi p thalat s whlch is freely o b vertible synthetic resin and a solvent therefor, in hyd enated petrcleum solvents. as d1stm the resin being catalytically and non-uniformly guished o t l y resin 0f Example advanced so that a part of it is gelled while part This p emented emulsion co ns 0. 5% 501- remains ungelled. the proportions of gelled to ids; the lacquer phase contains about 3% solids. ungelled resin being such as to produce a vehicle It may be blended with the pigmented emulsion 50 having a marked yieldivalue and variable flow of Example 3 in ratios of 1 to 1 and higher, characteristics in different parts thereof and conto produce a three-phase system in which a lowtaining smooth gelatinous masses of resin dissolids clear lacquer is the outer phase, and water persed in a solution of resin not advanced to the and resin-solvent aggregates bearing pigment are gel point, the entire composition having a yield the inner phases. Microscopic examination of the Value Of at least 50 dynes P q r centimeter. mixture indicates that the two disperse phases A textile decorating co p of P c are in very close contact with one another. The consistency such that it can be applied to cloth mixtures are stable, and prints made therewith by intaglio p gplates to produce visually show the same resistance to washing and other continuous but microscopically discontinuous influences as prints made from Exam le 3. d ati s n c th, w h c p s s pi m nt The new products we have described, when dispersed in a 'vehicle comprising a heat-conused for printing on fabric, give surface prints vertible synthetic resin and a solvent therefor, the with unusually good color value; they can be resin being catalytically and non-uniformly adconverted' to wash-fastness very much more vanced so that a part of it is gelled while part rapidly than can ungelled materials. remains ungelled, the proportions of gelled to containing smooth gelatinous masses of resin dispersed in a. solution of resirrnot advanced to the gel point, the entire composition having a yield value of at least 50 dynes per square centimeter.

3. The composition of claim 2, in which the resin is a cerbamide-aldehyde resin,

' 4. The composition of claim 2, in which the composition has water emulsified therein as a. discontinuous phase.

DAVID M. GANS. JOHN R. ABRAMS.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,016,180 Schmidt Oct. 1, 1935 2,064,875 Bender Oct. 22, 1936 2,109,291 Hovey et a] Feb. 22, 1938 2,222,581 Jenett Nov. 19, 1940 1,998,539 Gams Apr. 23, 1935 2,320,510 Corn-well June 1, 1943 2,332,939 Schmitz Oct. 26, 1943 

